Derivatives of oxycarbonic acid and process of making same.



UNrrnn STATES PATENT OFFICE.

ARTHUR EICI-IENGRUN, OF ELBERFELD, GERMANY, ASSIGNOR TO THEFARBENFABRIKEN OF ELBERFELD (30., OF NEW YORK, N. Y.

DERIVATlVES 0F OXYCARBONIC ACID AND PROCESS OF MAKING SAME.

SPECIFICATION forming part Of Letters Patent N0. 675,544, dated June 4,1901. Application filed August 5, 1899. Serial No. 726,26). (Specimens)To all whom, it may concern:

Be it known that I, ARTHUR Elonnnont'm, doctor of philosophy, chemist, acitizen of Germany, residing at Elberfeld, Germany, (assignor to theFARBENFABRIKEN or ELBER- FELD COMPANY, of New York,) have invented a newand usefullmprovement in the Manufacture of Derivatives of OxycarbonicAcid and Process of Making Same; and I hereby declare the following tobe a clear and exact description of my invention.

My invention relates to the production of new derivatives of aromaticoxycarbonic acids which are characterized by the fact that one of thehydrogen atoms of the benzol nucleus is substituted by the group -CH,X,(X meaning a halogen atom, such as chlorin, bromin, or iodin.)

As starting materials for my new compounds I can employ oxycarbonicacids of the benzene or naphthalene series-such as salicylic acid,paraoxybenzoic acid, the cresotinic acids, the oxynaphthoic acids, orthe like substances. In order to produce the abovedefined newderivatives, the said starting materials are subjected to the action ofhalogenmethylic alcohols (such as OH OLOH, 011 812011, OH I. OH) in thepresence of a suitable condensing agent, such as hydrochloric acid. Thenew products thus obtained are crystalline powders characterized by thefollowing reactions: \Vhen they are subjected to the action of hotwater, the halogen atom of the group 011 K is replaced by the hydroxygroup,andbodies containingthe group OH OH are produced. 'When they aresubjected to the action of alcohol, bodies containing the group (1H,.OR(R meaning an alkyl radical) are formed. A haloid acid, such ashydrochloric acid or the like, is set free during these two reactions.The new products are valuable remedies, for instance, for the purposesof dermatology.

I illustrate my new process by the following example: 1.238 kilos ofsalicylic acid are stirred into a solution of 0.665 kilos ofchlormethylic alcohol in five liters of highly-concentrated hydrochloricacid. The mixture is heated up to 20 to 40 centigrade and then allowedto stand for twelve hours. After this time a White pasty massresults,which is separated from the liquid by filtering and wash in gwith concentrated hydrochloric acid. The product is then dried at lowtemperatures and purified by crystallization from benzene. Thus it isobtained in the shape of brilliant leaves, which melt at 160 centigradeand are easily soluble in ether, acetone, acetic acid, acetic ether,benzene, and chloroform, soluble with difficulty in ligroin, insolublein petrolether and cold water.

The new product has most probably the formula:

0H,.Ol 0a ooon It exhibits the characteristic properties herc-= inbeforedefined. Thus, for instance, by the action of methylic alcohol it istransformed under evolution of hydrochloric acid into a methylic ethermelting at 103 centigrade. When heated with water, hydrochloric acid isset free, while the new compound is transformed into the known saligenincarbonic acid, having the formula:

melting at 14l2 centigrade.

The new compound is a Valuable remedy for skin diseases and is intendedto be used as a dustingpowder, &c. It is especially valuable in cases ofexcessive perspiration as a dusting-powder in the form of aten-per-cent. mixture with talcum.

In order to obtain the new product, it is not necessary to operate withfree chlormethylic alcohol. I obtain the same results on using thelatter in the so-called statu nasceudi-- viz, by employing instead ofchlormethylic alcohol a solution of this body which has been obtained bydissolving formic aldehyde in a concentrated hydrochloric acid andsaturating the resulting solution with gaseous hydrochloric acid. Theprocess proceeds in an analogous manner if instead of chlormethylicalcohol bromomethylic or iodomethylic alcohols are used.

Having now described my invention and in, what manner the same is to beperformed,

ICO

what I claim as new, and desire to secure by Letters Patent, is

1. The process for producing new derivatives of aromatic oxycarbonicacids containing the group -OH .X, X meaning a halogen atom whichprocess consists in first heating a mixture prepared from an aromaticoxycarbonic acid and a solution of a halogenmethylic alcohol inconcentrated hydrochlorlc acid, secondly isolating the products thusobtained by filtration and finally purifying the same, substantially ashereinbefore described.

2. The process for producing a new derivative from salicylic acid,having most probably the formula CH 01 c rn on \oooH whichprocessconsists in first heating a'mixture prepared from salicylic acid and asolutionjof chlormethylic alcohol in concentrated hydrochloric acid atfrom 20 to 40 centig'rade, secondly filtering 'off the resulting productand finally purifying the same substantially as hereinbefore described.

3. As new articles of manufacture the new derivatives of aromaticoxycarbonic acids which are characterized by the fact that they containthe group -OH X, X meaning a halogen atom, being crystalline powders,being transformed by the action of water into bodies containing thegroup '0H OH, being changed into compounds containing the group CH.OR, Rmeaning an alkyl radical if they are subjected to the action of alcoholsand which are insoluble in cold water and soluble in most organicsolvents, substantially as hereinbefore described.

4. As a new article of manufacture the new derivative from salicylicacid, having most probably the formula

